The Nanocrystalline Ceria Sol-Gel Coatings for High Temperature Applications

Sol-gel technology was utilized to produce nanocrystalline thin films of CeO₂ on substrates with different oxidation resistance at high temperatures. After deposition, the coatings were composed of CeO₂ crystallites with a size of 5 nm, randomly oriented on all the substrates. The annealing of gel deposited on Pt and Si substrates was accompanied by evaporation of water and other species and followed by growth of crystallites, without formation of any evident texture. Conversely, the annealing of coatings deposited on easy oxidizing substrates of Nr, Cr, or Ni−Cr alloys resulted in incorporation of CeO₂ crystallites into growing native oxide, and in slowing the oxidation rate. Examples of the application of CeO₂ ceramics as coatings deposited on selected metals and alloys for improving their oxidation performance are presented.     

Piperazine quaternary diammonium salts as additives to background electrolytes in capillary zone electrophoresis

The differential behavior of five different quaternary mono- and diammonium salts, among the 18 investigated, in modulating the electroendoosmotic flow (EOF) and analyte separations in capillary zone electrophoresis is evaluated. It is found that quaternary diammonium salts with positive charges separated by more than four carbon atoms, while exhibiting a very strong affinity for chromatographic silica beads, to the point of exhibiting Rf values close to zero, display, on the contrary, a very poor affinity for the silica wall of capillaries. Compounds separated only by a C2 unit (i.e., 1,4-dialkyl-1,4-diazoniabicyclo[2,2,2,]octane, salts 17 and 18) show high Rf values due to strong ion pair association. The unique behavior of quaternary monoammonium salts possessing an iodinated alkyl (butyl or octyl) tail (i.e., 1, 6, and 7) is attributed to their ability to be covalently affixed to the silica wall via alkylation of ionized silanols at alkaline pH values. They thus strongly modulate and typically invert the EOF, even when not present in the background electrolyte. On the contrary, all diammonium salts, devoid of such alkyl tails, are unable to modulate the EOF and to prevent analyte binding to the silica wall, since they are rapidly removed from the wall by the voltage gradient. However, if added in small amount to the background electrolyte, they offer excellent separations of mixtures of very similar organic acids and prevent any interaction with the capillary wall.     

Rapid separation of protein isoforms by capillary zone electrophoresis with new dynamic coatings

Many cellular functions are regulated through protein isoforms. Changes in the expression level or regulatory dysfunctions of isoforms often lead to developmental or pathological disorders. Isoforms are traditionally analyzed using techniques such as gel- or capillary-based isoelectric focusing. However, with proper electro-osmotic flow (EOF) control, isoforms with small pI differences can also be analyzed using capillary zone electrophoresis (CZE). Here we demonstrate the ability to quickly resolve isoforms of three model proteins (bovine serum albumin, transferrin, alpha1-antitrypsin) in capillaries coated with novel dynamic coatings. The coatings allow reproducible EOF modulation in the cathodal direction to a level of 10(-9) m2V(-1)s(-1). They also appear to inhibit protein adsorption to the capillary wall, making the isoform separations highly reproducible both in peak areas and apparent mobility. Isoforms of transferrin and alpha1-antitrypsin have been implicated in several human diseases. By coupling the CZE isoform separation with standard affinity capture assays, it may be possible to develop a cost-effective analytical platform for clinical diagnostics.     

Efficient and reproducible analysis of peptides by capillary electrophoresis using noncovalently bilayer-coated capillaries

The usefulness of a noncovalent capillary coating consisting of two layers of oppositely charged polymers for the separation of peptides with capillary electrophoresis (CE) was studied. Capillaries were coated simply by subsequently flushing with solutions of 1% m/v Polybrene and 1% v/v poly(vinylsulfonate) (PVS) forming a bilayer, which showed to produce a strong and highly reproducible electroosmotic flow (EOF) at low pH. Using this coating in combination with a background electrolyte (BGE) containing sodium phosphate (pH 2.5) and 0.01% v/v PVS, initially broadened and overlapping peaks were obtained for some test peptides. By omitting the PVS from the BGE, the peak width and shape of the peptides improved resulting in baseline separation. A systematic study of the influence of the BGE composition showed that considerable further enhancement of the separation efficiency was achieved by increasing the ionic strength of the BGE. Using a BGE of 200 mM tris(hydroxymethyl)aminomethane (Tris)-phosphate (pH 2.5) plate numbers for the peptides were in the 300 000-600 000 range and the relative standard deviation of the peptide migration times was less then 0.3% (n = 5). The use of Tris-phosphate instead of sodium phosphate allowed the current to stay within acceptable limits when 30 kV was used as separation voltage. Overall, the bilayer coating showed a remarkable EOF repeatability, as well as long-term stability. Compared to bare fused-silica capillaries the intraday and interday repeatability of migration times was very favorable and coated capillaries could be used for over a month performing analyses with low and high ionic strength BGEs without any performance deterioration. The usefulness of the bilayer-coated capillaries for the analysis of positively charged peptides was demonstrated by the fast and efficient separation of various closely related enkephalins and the baseline separation of an isomeric peptide/peptoid couple exhibiting efficiencies of over 550 000 plates.     

Dielectric sorption analysis of pigmented epoxy coatings UV degraded at elevated pressures

Pigmented epoxy coatings were UV degraded for various periods at elevated pressures (1-100 bar) and investigated with dielectric sorption analysis (DSA). Differences in dynamics of absorption behaviour for degraded polymer occurred due to increased hydrophilicity, crosslinking and porosity. Degradation at all pressures showed desorption, caused by swelling of the coating and shrinking of pore size. The amount of water sorption and desorption rose linearly from 1 bar to 50 bar and from 50 bar on no further increase in degradation was found. Longer degradation times at 100 bar also resulted in a linear trend. At lower frequencies double peaks were found as a result of water desorption, polymer relaxation, water-hydrophilic cluster interactions and polymer swelling, indicating a frequency dependence. The double peak could be fitted by two independent curves, whereas a single exponential term sufficed to fit the desorption of water for all frequencies. Pressure is clearly an accelerating degradation parameter in combination with an UV source.     

球磨形成的Ni-Mo纳米晶复合镀层上的析氢反应

采用复合电镀的方法将不同球磨时间制备的高催化活性的纳米晶，Ｎｉ－Ｍｏ合金粉直接镀于电极表面，并用稳态极化曲线及交流阻抗技术测试了这些电极析氢的电化学活性，同时用Ｘ射线衍射，透射电镜及扫描电镜监测了Ｎｉ－Ｍｏ合金粉的物相结构，晶粒尺寸及复合电极表面的形貌，并初步探讨了这些复合电极的析氢机理，实验结果表明，球磨不仅可使镍钼粉合金化成为纳米晶，同时随着球磨时间的增加，纳米晶晶粒继续细化，电极的析氢催化活     

Use of gamma-irradiation technology in combination with edible coating to produce shelf-stable foods

This research was undertaken to determine the effectiveness of low-dose gamma-irradiation combined with edible coatings to produce shelf-stable foods. Three types of commercially distributed food products were investigated: precooked shrimps, ready to cook pizzas, and fresh strawberries. Samples were coated with various formulations of protein-based solutions and irradiated at total doses between 0 and 3 kGy. Samples were stored at 4°C and evaluated periodically for microbial growth. Sensorial analysis was also performed using a nine-point hedonic scale to evaluate the organoleptic characteristics (odor, taste and appearance). The results showed significant (p0.05) combined effect of gamma-irradiation and coating on microbial growth (APCs and Pseudomonas putida). The shelf-life extension periods ranged from 3 to 10 days for shrimps and from 7 to 20 days for pizzas, compared to uncoated/unirradiated products. No significant (p>0.05) detrimental effect of gamma-irradiation on sensorial characteristics (odor, taste, appearance) was observed. In strawberries, coating with irradiated protein solutions resulted in significant reduction of the percentage of mold contamination.     

Effect of the Solvent on the Water Properties of Water/Oil Microemulsions

Porous poly(styrene-divinylbenzene) (PS-DVB) particles were modified by adsorption of hydrophobically-modified dextrans, to provide chromatographic matrices for biomolecule chromatography. The dextran distribution and the pore characteristics of various coated PS-DVB beads were examined using nitrogen adsorption–desorption, mercury intrusion, and size exclusion chromatography. It was found that the adsorption of dextran does not result in homogeneous layers but rather in inhomogeneous ones. At high dextran loading and high content of hydrophobic groups in the adsorbed polymer, most of the pores of the macroporous rigid material are filled with a soft and porous dextran network being stabilized by hydrophobic interactions. According to chromatographic experiments, most of the surface was nevertheless expected to be covered at least by a thin and dense protecting layer since proteins—even those that are small enough to penetrate the dextran network—cannot interact nonspecifically with the internal pore surface. At low content of hydrophobic groups, dextran deposits preferentially as a thicker and more diffuse layer. However, the thickness of the coating is expected to be irregular and probably contributes to an increase in the roughness of the polystyrene surface.     

建筑织物膜材双轴剪切试验与分析

为了研究建筑织物膜材的剪切力学性能,提出一种新的剪切测试方法。采用中心区域宽度和四臂长度均为16cm的十字形试件,试件纱线的经纬向与加载方向呈45°角。根据膜材变形和应力关系,推导了剪应力和剪应变的计算方法。定义了使试件中心区域产生三个循环剪应力场的加载谱,循环产生正负交替的剪切应力。试验采用表面抛光的(Polyvinylidene Fluoride,聚偏氟乙烯)涂层膜材,测量x、y两个方向的应力和应变,通过计算得到剪切应力应变曲线,并对试验结果进行分析。结果表明,新的剪切测试方法能够反映建筑织物膜材剪切力学性能。最后通过有限元方法模拟材料受剪状态下的应力和应变,与试验得到的应力值和应变值相近。